Non-diffusible magenta compound capable of releasing a 4-(2-heterocyclazo)phenol having a heterocyclic ring fused thereto

ABSTRACT

Nondiffusible compounds capable of releasing at least one diffusible magenta dye moiety having the formula: ##STR1## wherein: (a) X represents the atoms necessary to complete a 5- or 6-membered heterocyclic ring; 
     (b) Y represents the atoms necessary to complete a 5- or 6-membered heterocyclic fused ring; 
     (c) CAR represents a ballasted carrier moiety capable of releasing the diffusible magenta dye moiety as a function of development of a silver halide emulsion layer under alkaline conditions; 
     (d) R represents a hydroxy group, a salt thereof, or a hydrolyzable precursor thereof, or CAR which is linked to the dye moiety through an oxygen atom thereon; and 
     (e) n is 0, 1 or 2, with the proviso that when n is 0, then R is CAR which is linked to the dye moiety through an oxygen atom thereon.

CROSS-REFERENCE TO RELATED APPLICATION

This is a division of application Ser. No. 458,499, filed Jan. 17, 1983,now U.S. Pat. No. 4,420,550 issued Dec. 13, 1983, which is acontinuation-in-part of application Ser. No. 380,843, filed May 21,1982, now abandoned.

This invention relates to photography and more particularly to colordiffusion transfer photography employing certain nondiffusible magentadye-releasing compounds which, as a function of development of a silverhalide emulsion layer, release a diffusible magenta dye. Thedye-releasing compound can be premetallized or a metal complex of thereleased dye can be formed in an image-receiving layer.

U.S. Pat. No. 4,148,642 of Chapman et al discloses nondiffusiblecompounds having a releasable cyan 1-arylazo-4-isoquinolinol dye moiety.The compounds of our invention, however, are magenta and comprisedifferent heterocyclic moieties attached to an azo linkage than those ofChapman et al.

Various metallizable magenta dyes are described in U.S. Pat. No.4,207,104 of Chapman et al (pyridylazonaphthols), U.S. Pat. No.4,287,292 of Chapman et al (o-carboxyarylazopyridinediols) and U.S. Pat.No. 4,357,410 of Anderson et al[2-(pyridylazo)-5-(N-alkylanilino)phenols]. The magenta dye-releasingcompounds of our invention, however, have narrower band widths and lessunwanted absorption than these prior art metallizable dyes as will beshown by comparative tests hereinafter.

U.S. Pat. Nos. 2,218,231 and 2,234,724 relate to textile dyes comprisingazo compounds having a quinoline moiety. U.S. Pat. Nos. 3,389,132 and3,377,337 and French Pat. No. 1,270,940 relate to metal complexes of azodyes having a quinoline moiety, also used as textile dyes. There is nodisclosure in those patents, however, that the quinoline moiety may belinked through an azo linkage to a heterocyclic moiety, as describedherein. In addition, there is no disclosure in those references thatcarrier moieties could be attached to those compounds, or that theycould be premetallized or that they could be used in photographicelements.

Canadian Pat. No. 762,451 relates to metallizable textile dyescomprising compounds having a quinoline moiety linked through an azolinkage to a heterocyclic moiety. There is no disclosure in this patent,however, that a carrier moiety could be attached to those compounds tobe used as dye-releasers in photographic elements, or that they could bepremetallized or that quinolinol moieties could be employed, asdescribed herein.

In U.S. Pat. No. 4,076,529 issued Feb. 28, 1978, nondiffusible dyereleasing compounds are disclosed. Among the various dye moietiesdisclosed which can be released are "metal complexed dyes". No specificstructures are shown, however.

A premetallized azo dye attached to a ballasted carrier moiety whichreleases the dye as a function of development is disclosed in JapanesePublication No. 106727/1977. The specific compounds of our invention arenot disclosed, however.

U.S. Pat. No. 4,142,891 of Baigrie et al relates to variousnondiffusible azo dye-releasing compounds having a releasable azo dyemoiety. When the dye moiety is released, it diffuses to animage-receiving layer where it is then contacted with metal ions to forma stable metal complex. These dye-releasing compounds are described asbeing metallizable, i.e., that are capable of forming a metal complex atsome step in the process. In column 1, lines 40-45 of that patent,reference is made to the April 1977 edition of Research Disclosure,pages 32-39, which discloses "premetallized dyes" which "are largemolecules which diffuse more slowly than unmetallized dyes, resulting inlong access times for image formations." The specific compounds of ourinvention are not disclosed, however.

It would be desirable to provide improved magenta dye-releasingcompounds containing chelating dye moieties, so that the dye which isreleased imagewise during processing, which can be premetallized ormetallizable, can diffuse to an image-receiving layer to form ametal-complexed, dye transfer image having better hues, minimum unwantedabsorption outside the green region of the spectrum, narrowerbandwidths, rapid diffusion rates and shorter access times than those ofthe prior art, as well as good stability to heat, light and chemicalreagents.

A photographic element in accordance with one embodiment of theinvention comprises a support having thereon at least one photosensitivesilver halide emulsion layer having associated therewith a dyeimage-providing material comprising a non-diffusible compound capable ofreleasing at least one diffusible magenta dye moiety comprising an8-(2-heterocyclylazo)-5-quinolinol, the compound containing:

(a) in the heterocyclyl moiety a nitrogen atom which is adjacent to thepoint of attachement to the azo linkage; and

(b) a ballasted carrier moiety which is capable of releasing thediffusible azo dye under alkaline conditions.

In a preferred embodiment of our invention, our nondiffusible compoundsare capable of releasing at least one diffusible magenta dye moietycomprising a 4-(2-heterocyclylazo)phenol having a heterocyclic ringfused thereto, the compounds having the following formula: ##STR2##wherein:

(a) X represents the atoms necessary to complete a 5- or 6-memberedheterocyclic ring such as pyridine, imidazole, pyrazole, oxazole,thiazole, or thiazoline;

(b) Y represents the atoms necessary to complete a 5- or 6-memberedheterocyclic fused ring such as quinoline, quinoxaline, benzimidazole,or indolenine;

(c) CAR represents a ballasted carrier moiety capable of releasing thediffusible magenta dye moiety as a function of development of the silverhalide emulsion layer under alkaline conditions;

(d) R represents a hydroxy group, a salt thereof, or a hydrolyzableprecursor thereof, or CAR which is linked to the dye moiety through anoxygen atom thereon; and

(e) n is 0, 1 or 2, with the proviso that when n is 0, then R is CARwhich is linked to the dye moiety through an oxygen atom thereon.

In a preferred embodiment of our invention, R is hydroxy, X representsthe atoms necessary to complete a pyridine, imidazole or pyrazole ringand Y represents the atoms necessary to complete a quinoline,quinoxaline or benzimidazole ring. In another preferred embbodiment ofour invention, R is hydroxy, X represents the atoms necessary tocomplete a pyridine ring, Y represents the atoms necessary to complete aquinoline ring, n is 1 and CAR is attached to the pyridine ring.

As stated above, R can be a hydroxy group, a salt thereof such as asodium salt, a tetramethylammonium salt, etc., or a hydrolyzableprecursor thereof, or CAR as defined below. Hydrolyzable precursors of ahydroxy group which can be employed in our invention include acetate,benzoate, pivalate, carbamates, an acyloxy group having the formula--OCOR₁, --OCOOR₁ or --OCON(R₁)₂, wherein each R₁ is an alkyl grouphaving 1 to about 8 carbon atoms, such as methyl, ethyl, isopropyl,butyl and the like, or an aryl group having 6 to about 12 carbon atoms,such as phenyl, etc., or any of the blocking groups which can be cleavedby an intramolecular nucleophilic displacement reaction, as disclosed inMooberry and Archie U.S. Pat. No. 4,310,612, the disclosure of which ishereby incorporated by reference.

When R is CAR as defined below or a hydrolyzable precursor of a hydroxygroup, the absorption of the dye-releasing compound is shifted out ofthe green region of the spectrum, so that the compound may beincorporated in the emulsion layer, which is very desirable in certainembodiments of the invention.

In another embodiment of the invention, CAR may have attached theretotwo azo dye moieties in which case two dye moieties will be releasedfrom one CAR moiety.

Other substituents may also be present in the two rings illustratedabove, such as alkyl of 1 to 6 carbon atoms, acyl, aryl of 6 to 10carbon atoms, aralkyl, alkylsulfonyl, amino, alkoxy, halogens such aschloro or bromo, morpholino, phenylsulfamoyl, solubilizing groups suchas sulfonamido, sulfamoyl, carboxy, sulfo or hydrolyzable precursorsthereof.

In another preferred embodiment of our invention, the dyeimage-providing materials described above may be premetallized, i.e.,they would comprise a coordination complex of the nondiffusiblecompounds described above and a polyvalent metal ion. In yet anotherpreferred embodiment of the invention, the coordination complexcomprises a 2:1 complex of the nondiffusible compound and a divalent ortrivalent hexacoordinate metal ion. Such metal ions include, forexample, zinc(II), nickel(II), copper(II), cobalt(II) and cobalt(III)ions. Especially good results are obtained with nickel(II) ions.

There is great latitude in selecting a CAR moiety which is attached tothe dye-releasing compounds described above. Depending upon the natureof the ballasted carrier selected, various groups may be needed toattach or link the carrier moiety to the dye. Such linking groups areconsidered to be a part of the CAR moiety in the above definition. Itshould also be noted that, when the dye moiety is released from thecompound, cleavage may take place in such a position that part or all ofthe linking group, if one is present, and even part of the ballastedmoiety, may be transferred to the image-receiving layer, along with thedye moiety. In any event, the dye nucleus as shown above can be thoughtof as the minimum which is transferred.

CAR moieties useful in the invention are described in U.S. Pat. Nos.3,227,550; 3,628,952; 3,227,552 and 3,844,785 (dye released bychromogenic coupling); U.S. Pat. Nos. 3,443,939 and 3,443,940 (dyereleased by intramolecular ring closure); U.S. Pat. Nos. 3,698,897 and3,725,062 (dye released from hydroquinone derivatives); U.S. Pat. No.3,728,113 (dye released from a hydroquinonylmethyl quaternary salt);U.S. Pat. Nos. 3,719,489 and 3,443,941 (silver ion induced dye release);British Patent Publication 2,017,950A (dye released by a dye bleachprocess); U.S. Pat. Nos. 4,053,312; 4,198,235; 4,179,231; 4,055,428 and4,149,892 (dye released by oxidation and deamidation); and U.S. Pat.Nos. 3,245,789 and 3,980,497; Canadian Pat. No. 602,607; British Pat.No. 1,464,104; Research Disclosure 14447, April 1976; U.S. Pat. No.4,139,379 of Chasman et al, U.S. Pat. No. 4,232,107 and European PatentPublication 12908 (dye released by miscellaneous mechanisms), thedisclosures of which are hereby incorporated by reference.

When R is CAR, it must be one which is linked to the dye moiety throughan oxygen atom thereon, so that a phenol having a heterocyclic ringfused thereto is released from the nondiffusible compound under alkalineconditions. Such CARs are disclosed, for example, in U.S. Pat. No.4,139,379, discussed above.

In a further preferred embodiment of the invention, the ballastedcarrier moiety or CAR as described above may be represented by thefollowing formula:

    (Ballast-Carrier-Link)--

wherein:

(a) Ballast is an organic ballasting radical of such molecular size andconfiguration as to render said compound nondiffusible in saidphotographic element during development in an alkaline processingcomposition;

(b) Carrier is an oxidizable acyclic, carbocyclic or heterocyclic moiety(see "The Theory of the Photographic Process", by C. E. K. Mees and T.H. James, Third Edition, 1966, pages 282 to 283), e.g., moietiescontaining atoms according to the following configuration:

    a(--C═C).sub.b --

wherein:

b is a positive integer of 1 to 2; and

a represents the radicals OH, SH, NH-- or hydrolyzable precursorsthereof; and

(c) Link represents a group which, upon oxidation of said Carriermoiety, is capable of being hydrolytically cleaved to release thediffusible azo dye. For example, Link may be the following groups:##STR3## wherein * represents the position of attachment to Carrier.

The Ballast group in the above formula is not critical, so long as itconfers nondiffusibility to the compound. Typical Ballast groups includelong-chain alkyl radicals, as well as aromatic radicals of the benzeneand naphthalene series linked to the compound. Useful Ballast groupsgenerally have at least 8 carbon compounds, such as substituted orunsubstituted alkyl groups of 8 to 22 carbon atoms; a carbamoyl radicalhaving 8 to 30 carbon atoms, such as --CONH(CH₂)₄ --O--C₆ H₃ (C₅ H₁₁)₂or --CON(C₁₂ H₂₅)₂ ; or a keto radical having 8 to 30 carbon atoms, suchas --CO--C₁₇ H₃₅ or --CO--C₆ H₄ (t-C₁₂ H₂₅).

For specific examples of Ballast-Carrier moieties useful as the CARmoiety in this invention, reference is made to the November 1976 editionof Research Disclosure, pages 68 through 74, and the April 1977 editionof Research Disclosure, pages 32 through 39, the disclosures of whichare hereby incorporated by reference.

In a highly preferred embodiment of the invention, the ballasted carriermoiety or CAR in the above formula is a group having the formula:##STR4## wherein:

(a) Ballast is an organic ballasting radical of such molecular size andconfiguration (e.g., simple organic groups or polymeric groups) as torender said compound nondiffusible in a photographic element duringdevelopment in an alkaline processing composition;

(b) D is OR¹ or NHR² wherein R¹ is hydrogen or a hydrolyzable moiety,such as acetyl, mono-, di- or trichloroacetyl radicals, perfluoroacyl,pyruvyl, alkoxyacyl, nitrobenzoyl, cyano-benzolyl, sulfonyl or sulfinyl,and R² is hydrogen or a substituted or unsubstituted alkyl group of 1 to22 carbon atoms, such as methyl, ethyl, hydroxyethyl, propyl, butyl,secondary butyl, tertbutyl, cyclopropyl, 4-chlorobutyl, cyclobutyl,4-nitroamyl, hexyl, cyclohexyl, octyl, decyl, octadecyl, dodecyl, benzylor phenethyl (when R² is an alkyl group of greater than 8 carbon atoms,it can serve as a partial or sole Ballast);

(c) Z represents at least the atoms necessary to complete a benzenenucleus, a naphthalene nucleus, or a 5 to 7 membered heterocyclic ring,such as pyrazolone or pyrimidine; and

(d) j is a positive integer of 1 to 2 and is 2 when D is OR¹ or when R²is hydrogen or an alkyl group of less than 8 carbon atoms.

Especially good results are obtained in the above formula when D is OH,j is 2, and Y is a naphthalene nucleus.

Examples of the CAR moiety in this highly preferred embodiment aredisclosed in U.S. Pat. Nos. 4,076,529; 3,993,638 and 3,928,312, thedisclosures of which are hereby incorporated by reference, and includethe following: ##STR5##

In another highly preferred embodiment of the invention, the ballastedcarrier moiety or CAR in the above formulas is such that the diffusibleazo dye is released as an inverse function of development of the silverhalide emulsion layer under alkaline conditions. This is ordinarilyreferred to as positive-working dye-release chemistry. In one of theseembodiments, the ballasted carrier moiety or CAR in the above formulasmay be a group having the formula: ##STR6## wherein:

Ballast is an organic ballasting radical of such molecular size andconfiguration as to render said compound nondiffusible in a photographicelement during development in an alkaline processing composition;

W¹ represents at least the atoms necessary to complete a benzene nucleus(including various substituents thereon); and

R³ is an alkyl (including substituted alkyl) radical having 1 to about 4carbon atoms.

Examples of the CAR moiety in this formula (I) include the following:##STR7##

In a second embodiment of positive-working dye-release chemistry asreferred to above, the ballasted carrier moiety or CAR in the aboveformulas may be a group having the formula: ##STR8## wherein:

Ballast is an organic ballasting radical of such molecular size andconfiguration as to render said compound nondiffusible in a photographicelement during development in an alkaline processing composition;

W² represents at least the atoms necessary to complete a quinone nucleus(including various substituents thereon);

r is a positive integer of 1 or 2;

R⁴ is an alkyl (including substituted alkyl) radical having 1 to about40 carbon atoms or an aryl (including substituted aryl) radical having 6to about 40 carbon atoms; and

k is a positive integer of 1 to 2 and is 2 when R⁴ is a radical of lessthan 8 carbon atoms.

Examples of the CAR moiety in this formula (II) include the following:##STR9##

In using the compounds in formulas I and II above, they are employed ina photographic element similar to the other nondiffusible dye-releasersdescribed previously. Upon reduction of the compound as a function ofsilver halide development under alkaline conditions, the metallizableazo dye is released. In this embodiment, conventional negative-workingsilver halide emulsions, as well as direct-positive emulsions, can beemployed. For further details concerning these particular CAR moieties,including synthesis details, reference is made to U.S. Pat. No.4,139,379 of Chasman et al, the disclosure of which is herebyincorporated by reference.

In a third embodiment of positive-working dye-release chemistry asreferred to above, the ballasted carrier moiety or CAR in the aboveformulas may be a group having the formula: ##STR10## wherein:

Ballast, W¹ and R³ are as defined for formula (I) above.

Examples of the CAR moiety in this formula (III) include the following:##STR11##

For further details concerning this particular CAR moiety, includingsynthesis details, reference is made to U.S. Pat. No. 4,199,354 ofHinshaw et al, the disclosure of which is hereby incorporated byreference.

In a fourth embodiment of positive-working dye-release chemistry asreferred to above, the ballasted carrier moiety or CAR in the aboveformulas may be a group having the formula: ##STR12## wherein:

Ballast, r, R⁴ and k are as defined for formula (II) above;

W¹ is as defined for formula (I) above; and

K is OH or a hydrolyzable precursor thereof.

Examples of the CAR moiety in this formula (IV) include the following:##STR13##

For further details concerning this particular CAR moiety, includingsynthesis details, reference is made to U.S. Pat. No. 3,980,479 ofFields et al, the disclosure of which is hereby incorporated byreference.

Representative compounds included within the scope of the inventioninclude the following: ##STR14##

A process for producing a photographic transfer image in color accordingto the invention comprises:

(a) treating an imagewise-exposed photographic element as describedabove having a metallizable dye-releasing compound with an alkalineprocessing composition in the presence of a silver halide developingagent to effect development of each of the exposed silver halideemulsion layers;

(b) the dye-releasing compound then releasing the diffusible azo dye asdescribed above imagewise as a function of the development of each ofthe silver halide emulsion layers;

(c) at least a portion of the imagewise distribution of the azo dyediffusing to a dye image-receiving layer; and

(d) contacting the imagewise distribution of azo dye with metal ions,thereby forming a metal-complexed azo dye transfer image.

The magenta azo dye moiety which is released from the metallizabledye-releasing compounds described above is a tridentate ligand and willform a coordination complex in the image-receiving layer with polyvalentmetal ions. The mtal ions can be present in the image-receiving layeritself or in a layer adjacent thereto, or the image-receiving layer canbe contacted with metal ions in a bath after diffusion of the dye hastaken place. Metal ions most useful in the invention are those which areessentially colorless when incorporated into the image-receivingelement, are inert with respect to the silver halide layers, reactreadily with the released dye to form a complex of the desired hue, aretightly coordinated to the dye in the complex, have a stable oxidationstate, and form a dye complex which is stable to heat, light andchemical reagents. In general, good results are obtained with polyvalentmetal ions such as copper (II), zinc (II), nickel (II), platinum (II),palladium (II), cobalt (II) and cobalt (III) ions.

For example, it is believed that the coordination complex which isformed from the tridentate, metallizable azo dye ligand according to theinvention in one of the preferred embodiments thereof has the followingstructure: ##STR15## wherein:

X and Y are as defined above;

Me is metal; and

Lig is one or more ligand groups, depending upon the coordination numberof the metal ion, such as H₂ O, Cl or pyridine, a second dye moiety or apart of a polymer. (A divalent metal ion in solution always has a numberof ligand groups attached to it depending upon its coordination numberand the relative reactivity of various ligand groups such as water,ammonia, chloride, pyridine or acetate, which may be in the solutionenvironment of the metal ion. These ligands can be displaced by atridentate azo dye ligand which would form a more stable complex.)

Thus, in accordance with this preferred embodiment of the invention, aphotographic element is provided which comprises a support havingthereon a coordination complex of a polyvalent metal ion and a compoundhaving the formula: ##STR16## wherein:

X and Y are as described previously.

The element usually contains a photographic mordant or image-receivinglayer to bind the dye or coordination complex thereto.

The structures shown above may also, of course, be substituted in thesame manner as described above for the starting compounds from whichthey are released.

It will be appreciated that, after processing the photographic elementdescribed above, there remains in it after transfer has taken place animagewise distribution of azo dye in addition to developed silver. Acolor image comprising residual nondiffusible compound is obtained inthis element if the residual silver and silver halide are removed by anyconventional manner well known to those skilled in the photographic art,such as a bleach bath, followed by a fix bath, a bleach-fix bath, etc.Such a retained dye image should normally be treated with metal ions tometallize the dyes to increase their light fastness and shift theirspectral absorption to the intended region. The imagewise distributionof azo dye may also diffuse out of the element into these baths, ifdesired, rather than to an image-receiving element. If anegative-working silver halide emulsion is employed in certain preferredphotosensitive elements, described above, then a positive color image,such as a reflection print, a color transparency or motion picture film,is produced in this manner. If a direct-positive silver halide emulsionis employed in such photosensitive elements, then a negative color imageis produced.

The photographic element in the above-described process can be treatedin any manner with an alkaline processing composition to effect orinitiate development. A preferred method for applying processingcomposition is by use of a rupturable container or pod which containsthe composition. In general, the processing composition employed in thisinvention contains the developing agent for development, although thecomposition could also just be an alkaline solution where the developeris incorporated in the photographic element, image-receiving element orprocess sheet, in which case the alkaline solution serves to activatethe incorporated developer.

A photographic film unit or assemblage in accordance with this inventionis adapted to be processed by an alkaline processing composition, andcomprises:

(1) a photographic element as described above; and

(2) a dye image-receiving layer.

In this embodiment, the processing composition may be inserted into thefilm unit, such as by interjecting processing solution withcommunicating members similar to hypodermic syringes which are attachedeither to a camera or camera cartridge. The processing composition canalso be applied by means of a swab or by dipping in a bath, if sodesired. Another method of applying processing composition in a filmassemblage which can be used in our invention is the liquid spreadingmeans described in U.S. Application Ser. No. 143,230 of Columbus, filedApr. 24, 1980, now U.S. Pat. No. 4,370,407, issued Jan. 25, 1983.

In a preferred embodiment of the invention, the assemblage itselfcontains the alkaline processing composition and means containing samefor discharge within the film unit. There can be employed, for example,a rupturable container which is adapted to be positioned duringprocessing of the film unit so that a compressive force applied to thecontainer by pressure-applying members, such as would be found in acamera designed for in-camera processing, will effect a discharge of thecontainer's contents within the film unit.

In the embodiment described above, the dye image-receiving layer mayitself contain metal ions or the metal ions may be present in anadjacent layer, so that the tridentate, metallizable azo dye ligandwhich is released will form a coordination complex therewith. The dyethus becomes immobilized in the dye image-receiving layer and metallizedat the same time. Alternatively, the dye image in the dyeimage-receiving layer may be treated with a solution containing metalions to effect metallization. The formation of the coordination complexshifts the absorption of the dye to the desired hue, usually to longerwavelengths, which have a different absorption than that of the initialdye-releasing compound. If this shift is large enough, then thedye-releasing compound may be incorporated in a silver halide emulsionlayer without adversely affecting its sensitivity.

The dye image-receiving layer in the above-described film assemblage isoptionally located on a separate support adapted to be superposed on thephotographic element after exposure thereof. Such image-receivingelements are generally disclosed, for example, in U.S. Pat. No.3,362,819. When this means for discharging the processing composition isa rupturable container, it is usually positioned in relation to thephotographic element and the image-receiving element so that acompressive force applied to the container by pressure-applying members,such as would be found in a typical camera used for in-cameraprocessing, will effect a discharge of the container's contents betweenthe image-receiving element and the outermost layer of the photographicelement. After processing, the dye image-receiving element is separatedfrom the photographic element.

The dye image-receiving layer in the above-described film assemblage inanother embodiment is located integrally with the photographic elementbetween the support and the lowermost photosensitive silver halideemulsion layer. One useful format for integral receiver-negativephotographic elements is disclosed in Belgian Pat. No. 757,960. In suchan embodiment, the support for the photographic element is transparentand is coated with an image-receiving layer, a substantially opaquelight-reflective layer, e.g., TiO₂, and then the photosensitive layer orlayers described above. After exposure of the photographic element, arupturable container containing an alkaline processing composition andan opaque process sheet are brought into superposed position.Pressure-applying members in the camera rupture the container and spreadprocessing composition over the photographic element as the film unit iswithdrawn from the camera. The processing composition develops eachexposed silver halide emulsion layer and dye images are formed as afunction of development which diffuse to the image-receiving layer toprovide a positive, right-reading image which is viewed through thetransparent support on the opaque reflecting layer background. For otherdetails concerning the format of this particular integral film unit,reference is made to the above-mentioned Belgian Pat. No. 757,960.

Another format for integral negative-receiver photographic elements inwhich the present invention is useful is disclosed in Canadian Pat. No.928,559. In this embodiment, the support for the photographic element istransparent and is coated with the image-receiving layer, asubstantially opaque, light-reflective layer and the photosensitivelayer or layers described above. A rupturable container containing analkaline processing composition and an opacifier is positioned adjacentthe top layer and a transparent top sheet which has thereon aneutralizing layer and a timing layer. The film unit is placed in acamera, exposed through the transparent top sheet and then passedthrough a pair of pressure-applying members in the camera as it is beingremoved therefrom. The pressure-applying members rupture the containerand spread processing composition and opacifier over the negativeportion of the film unit to render it light-insensitive. The processingcomposition develops each silver halide layer and dye images are formedas a result of development which diffuse to the image-receiving layer toprovide a positive, right-reading image which is viewed through thetransparent support on the opaque reflecting layer background. Forfurther details concerning the format of this particular integral filmunit, reference is made to the above-mentioned Canadian Pat. No.928,559.

Still other useful integral formats in which this invention can beemployed are described in U.S. Pat. Nos. 3,415,644; 3,415,645;3,415,646; 3,647,437 and 3,635,707. In most of these formats, aphoto-sensitive silver halide emulsion is coated on an opaque supportand a dye image-receiving layer is located on a separate transparentsupport superposed over the layer outermost from the opaque support. Inaddition, this transparent support also preferably contains aneutralizing layer and a timing layer underneath the dye image-receivinglayer.

In another embodiment of the invention, a neutralizing layer and timinglayer are located underneath the photosensitive layer or layers. In thatembodiment, the photographic element would comprise a support havingthereon, in sequence, a neutralizing layer, a timing layer and at leastone photosensitive silver halide emulsion layer having associatedtherewith a dye-releasing compound as described above. A dyeimage-receiving layer as described above would be provided on a secondsupport with the processing composition being applied therebetween. Thisformat could either be integral or peel-apart as described above.

Another embodiment of the invention uses the image-reversing techniquedisclosed in British Pat. No. 904,364, page 19, lines 1 through 41. Inthis process, the dye-releasing compounds are used in combination withphysical development nuclei in a nuclei layer contiguous to thephotosensitive silver halide emulsion layer. The film unit contains asilver halide solvent, preferably in a rupturable container with thealkaline processing composition.

The film unit or assembly used in the present invention is used toproduce positive images in single- or multicolors. In a three-colorsystem, each silver halide emulsion layer of the film assembly will haveassociated therewith a dye-releasing compound which releases a dyepossessing a predominant spectral absorption within the region of thevisible spectrum to which said silver halide emulsion is sensitive(initially or after forming the coordination complex), i.e., theblue-sensitive silver halide emulsion layer will have a yellow oryellow-forming dye-releaser associated therewith, the green-sensitivesilver halide emulsion layer will have the magenta or magenta-formingdye-releaser of the invention associated therewith, and thered-sensitive silver halide emulsion layer will have a cyan orcyan-forming dye-releaser associated therewith. The dye-releaserassociated with each silver halide emulsion layer is contained either inthe silver halide emulsion layer itself or in a layer contiguous to thesilver halide emulsion layer.

The concentration of the dye-releasing compounds that are employed inthe present invention may be varied over a wide range, depending uponthe particular compound employed and the results which are desired. Forexample, the dye-releasers of the present invention may be coated inlayers at a concentration of about 0.1 to about 3 g/m² by using coatingsolutions containing between about 0.5 and about 8 percent by weight ofthe dye-releaser distributed in a hydrophilic film-forming naturalmaterial or synthetic polymer, such as gelatin, polyvinyl alcohol, etc,which is adapted to be permeated by aqueous alkaline processingcomposition.

Depending upon which CAR is used in the present invention, a variety ofsilver halide developing agents or electron transfer agents (ETA's) areuseful in this invention. In certain embodiments of the invention, anyETA can be employed as long as it cross-oxidizes with the dye-releasersdescribed herein. The ETA may also be incorporated in the photosensitiveelement to be activated by the alkaline processing composition. Specificexamples of ETA's useful in this invention include hydroquinonecompounds, such as hydroquinone, 2,5-dichlorohydroquinone or2-chlorohydroquinone; aminophenol compounds, such as 4-aminophenol,N-methylaminophenol, N,N-dimethylaminophenol, 3-methyl-4-aminophenol or3,5-dibromoaminophenol; catechol compounds, such as catechol,4-cyclohexylcatechol, 3-methoxycatechol or 4-(N-octadecylamino)catechol;and phenylenediamine compounds, such as N,N-N',N'-tetramethyl-p-phenylenediamine. In highly preferred embodiments, theETA is a 3-pyrazolidinone compound, such as 1-phenyl-3-pyrazolidinone(Phenidone), 1-phenyl-4,4-dimethyl-3-pyrazolidinone (Dimezone),4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidinone,4-hydroxymethyl-4-methyl-1-p-tolyl-3-pyrazolidinone,4-hydroxymethyl-4-methyl-1-(3,4-dimethylphenyl)-3-pyrazolidinone,1-m-tolyl-3-pyrzolidinone, 1-p-tolyl-3-pyrazolidinone,1-phenyl-4-methyl-3-pyrazolidinone, 1-phenyl-5-methyl-3-pyrazolidinone,1-phenyl-4,4-dihydroxymethyl-3-pyrazolidinone,1,4-dimethyl-3-pyrazolidinone, 4-methyl-3-pyrazolidinone,4,4-dimethyl-3-pyrazolidinone,1-(3-chlorophenyl)-4-methyl-3-pyrazolidinone,1-(4-chlorophenyl)-4-methyl-3-pyrazolidinone,1-(3-chlorophenyl)-3-pyrazolidinone,1-(4-chlorophenyl)-3-pyrazolidinone,1-(4-tolyl)-4-methyl-3-pyrazolidinone,1-(2-tolyl)-4-methyl-3-pyrazolidinone, 1-(4-tolyl)-3-pyrazolidinone,1-(3-tolyl)-3-pyrazolidinone, 1-(3-tolyl)-4,4-dimethyl-3-pyrazolidone,1-(2-trifluoroethyl)-4,4-dimethyl- 3-pyrazolidinone or5-methyl-3-pyrazolidone. A combination of different ETA's, such as thosedisclosed in U.S. Pat. No. 3,039,869, can also be employed. These ETA'sare employed in the liquid processing composition or contained, at leastin part, in any layer or layers of the photographic element or film unitto be activated by the alkaline processing composition, such as in thesilver halide emulsion layers, the dye image-providing material layers,interlayers, image-receiving layer, etc.

In a preferred embodiment of the invention, the silver halide developeror ETA employed in the process becomes oxidized upon development andreduces silver halide to silver metal. The oxidized developer thancross-oxidizes the dye-releasing compound. The product ofcross-oxidation then undergoes alkaline hydrolysis, thus releasing animagewise distribution of diffusible azo dye which then diffuses to thereceiving layer to provide the dye image. The diffusible moiety istransferable in alkaline processing composition either by virtue of itsself-diffusivity or by its having attached to it one or moresolubilizing groups, for example, a carboxy, sulpho, sulphonamido,hydroxy or morpholino group.

In using the dye-releasing compounds according to the invention whichproduce diffusible dye images as a function of development, eitherconventional negative-working or direct-positive silver halide emulsionsare employed. If the silver halide emulsion employed is adirect-positive silver halide emulsion, such as an internal-imageemulsion designed for use in the internal image reversal process or afogged, direct-positive emulsion such as a solarizing emulsion, which isdevelopable in unexposed areas, a positive image can be obtained incertain embodiments on the dye image-receiving layer. After exposure ofthe film unit, the alkaline processing composition permeates the variouslayers to initiate development of the exposed photosensitive silverhalide emulsion layers. The developing agent present in the film unitdevelops each of the silver halide emulsion layers in the unexposedareas (since the silver halide emulsions are direct-positive ones), thuscausing the developing agent to become oxidized imagewise correspondingto the unexposed areas of the direct-positive silver halide emulsionlayers. The oxidized developing agent then crossoxidizes thedye-releasing compounds and the oxidized form of the compounds thenundergoes a base-catalyzed reaction to release the dyes imagewise as afunction of the imagewise exposure of each of the silver halide emulsionlayers. At least a portion of the imagewise distributions of diffusibledyes diffuse to the image-receiving layer to form a positive image ofthe original subject. After being contacted by the alkaline processingcomposition, a neutralizing layer in the film unit or image-receivingunit lowers the pH of the film unit or image receiver to stabilize theimage.

Internal-image silver halide emulsions useful in this invention aredescribed more fully in the November 1976 edition of ResearchDisclosure, pages 76 through 79, the disclosure of which is herebyincorporated by reference.

The various silver halide emulsion layers of a color film assemblyemployed in this invention are disposed in the usual order, i.e., theblue-sensitive silver halide emulsion layer first with respect to theexposure side, followed by the green-sensitive and red-sensitive silverhalide emulsion layers. If desired, a yellow dye layer or a yellowcolloidal silver layer can be present between the blue-sensitive andgreen-sensitive silver halide emulsion layers for absorbing or filteringblue radiation that is transmitted through the blue-sensitive layer. Ifdesired, the selectively sensitized silver halide emulsion layers can bedisposed in a different order, e.g., the blue-sensitive layer first withrespect to the exposure side, followed by the red-sensitive andgreen-sensitive layers.

The rupturable container employed in certain embodiments of thisinvention is disclosed in U.S. Pat. Nos. 2,543,181; 2,643,886;3,654,732; 2,723,051; 3,056,492; 3,056,491 and 3,152,515. In general,such containers comprise a rectangular sheet of fluid-and air-imperviousmaterial folded longitudinally upon itself to form two walls which aresealed to one another along their longitudinal and end margins to form acavity in which processing solution is contained.

Generally speaking, except where noted otherwise, the silver halideemulsion layers employed in the invention comprise photosensitive silverhalide dispersed in gelatin and are about 0.6 to 6 microns in thickness;the dye-releasers are dispersed in an aqueous alkalinesolution-permeable polymeric binder, such as gelatin, as a separatelayer about 0.2 to 7 microns in thickness; and the alkalinesolutioon-permeable polymeric interlayers, e.g., gelatin, are about 0.2to 5 microns in thickness. Of course, these thicknesses are approximateonly and can be modified according to the product desired.

Scavengers for oxidized developing agent can be employed in variousinterlayers of the photographic elements of the invention. Suitablematerials are disclosed on page 83 of the November 1976 edition ofResearch Disclosure, the disclosure of which is hereby incorporated byreference.

Any material is useful as the image-receiving layer in this invention aslong as the desired function of mordanting or otherwise fixing the dyeimages is obtained. The particular material chosen will, of course,depend upon the dye to be mordanted. Suitable materials are disclosed onpages 80 through 82 of the November 1976 edition of Research Disclosure,the disclosure of which is hereby incorporated by reference.

Use of a neutralizing material in the film units employed in thisinvention will usually increase the stability of the transferred image.Generally, the neutralizing material will effect a reduction in the pHof the image layer from about 13 or 14 to at least 11 and preferably 5to 8 within a short time after imbibition. Suitable materials and theirfunctioning are disclosed on pages 22 and 23 of the July 1974 edition ofResearch Disclosure, and pages 35 through 37 of the July 1975 edition ofResearch Disclosure, the disclosures of which are hereby incorporated byreference.

A timing or inert spacer layer can be employed in the practice of thisinvention over the neutralizing layer which "times" or controls the pHreduction as a function of the rate at which alkali diffuses through theinert spacer layer. Examples of such timing layers and their functioningare disclosed in the Research Disclosure articles mentioned in theparagraph above concerning neutralizing layers.

The alkaline processing composition employed in this invention is theconventional aqueous solution of an alkaline material, e.g., alkalimetal hydroxides or carbonates such as sodium hydroxide, sodiumcarbonate or an amine such as diethylamine, preferably possessing a pHin excess of 11, and preferably containing a developing agent asdescribed previously. Suitable materials and addenda frequently added tosuch compositions are disclosed on pages 79 and 80 of the November 1976edition of Research Disclosure, the disclosure of which is herebyincorporated by reference.

The alkaline solution-permeable, substantially, opaque, light-reflectivelayer employed in certain embodiments of photographic film units used inthis invention is described more fully in the November 1976 edition ofResearch Disclosure, page 82, the disclosure of which is herebyincorporated by reference.

The supports for the photographic elements used in this invention can beany material as long as it does not deleteriously affect thephotographic properties of the film unit and is dimensionally stable.Typical flexible sheet materials are described on page 85 of theNovember 1976 edition of Research Disclosure, the disclosure of which ishereby incorporated by reference.

While the invention has been described with reference to layers ofsilver halide emulsions and dye image-providing materials, dotwisecoating, such as would be obtained using a gravure printing technique,could also be employed. In this technique, small dots of blue-, green-and red-sensitive emulsions have associated therewith, respectively,dots of yellow, magenta and cyan color-providing substances. Afterdevelopment, the transferred dyes would tend to fuse together into acontinuous tone. In an alternative embodiment, the emulsions sensitiveto each of the three primary regions of the spectrum can be disposed asa single segmented layer, e.g., as by the use of microvessels, asdescribed in Whitmore U.S. Patent Application Ser. No. 184,714, filedSeptember 8, 1980, now U.S. Pat. No. 4,362,804, issued December 7, 1982.

The silver halide emulsions useful in this invention, bothnegative-working and direct-positive ones, are well known to thoseskilled in the art and are described in Research Disclosure, Volume 176,December 1978, Item No. 17643, pages 22 and 23, "Emulsion preparation oftypes"; they are usually chemically and spectrally sensitized asdescribed on page 23, "Chemical sensitization", and "Spectralsensitization and desensitization", of the above article; they areoptionally protected against the production of fog and stabilizedagainst loss of sensitivity during keeping by employing the materialsdescribed on pages 24 and 25, "Antifoggants and stabilizers", of theabove article; they usually contain hardeners and coating aids asdescribed on page 26, "Hardeners", and pages 26 and 27, "Coating aids",of the above article; they and other layers in the photographic elementsused in this invention usually contain plasticizers, vehicles and filterdyes described on page 27, "Plasticizers and lubricants"; page 26,"Vehicles and vehicle extenders"; and pages 25 and 26, "Absorbing andscattering materials", of the above article; they and other layers inthe photographic elements used in this invention can contain addendawhich are incorporated by using the procedures described on page 27,"Methods of addition", of the above article; and they are usually coatedand dried by using the various techniques described on pages 27 and 28,"Coating and drying procedures", of the above article, the disclosuresof which are hereby incorporated by reference.

The term "nondiffusing" used herein has the meaning commonly applied tothe term in photography and denotes materials that, for all practicalpurposes, do not migrate or wander through organic colloid layers, suchas gelatin, in the photographic elements of the invention in an alkalinemedium and preferably when processed in a medium having a pH of 11 orgreater. The same meaning is to be attached to the term "immobile". Theterm "diffusible" as applied to the materials of this invention has theconverse meaning and denotes materials having the property of diffusingeffectively through the colloid layers of the photographic elements inan alkaline medium. "Mobile" has the same meaning as "diffusible".

The term "associated therewith" as used herein is intended to mean thatthe materials can be in either the same or different layers, so long asthe materials are accessible to one another.

The following examples are provided to further illustrate the invention.

EXAMPLE 1 Released Dyes--Spectra, Light Stability and Dye DiffusionTests

A receiving element was prepared comprising a poly(ethyleneterephthalate) film support having thereon a nickel sulfate hexahydrate(0.58 g/m²)/-gelatin (1.08 g/m²) metal complexing layer, and apoly(4-vinylpyridine)/gelatin mordant layer (each at 2.15 g/m²).

An alternative receiving element was used with the premetallizeddye-complexes. It comprised a poly(ethylene terephthalate) film supporthaving thereon a layer of gelatin (1.1 g/m²) and a mordant layer ofpoly(styrene-co-1-vinylimidazole-co-3-benzyl-1-vinylimidazolium chloride(50:40:10) (4.5 g/m²) and gelatin (2.2 g/m²).

The appropriate receiving element was immersed in an alkaline solutionof the azo dyes listed in Table I below. The receiver was removed fromthe dye solution, washed in distilled water, placed in a pH 7.0 buffersolution and dried. Transmission spectra obtained on each sample of themordanted dyes were normalized by computer to a density of 1.0. Thecharacteristic wavelength of the dye, λ_(1/2) in nm, is the mean of thewavelength limits of the absorption envelope at half the maximumdensity. The HBW ("half band width") in nm is the range or distancebetween those limits. The dye solution spectrum in 3:1 dioxane:water atpH 7 in the presence of excess nickel ion is also given.

The above receiving elements at pH 7 were then subjected to 10 daysirradiation by a high intensity daylight (HID), 6000 W Xenon arc lamp,the sample receiving 50,000 lux through a Wratten 2B (ultraviolet)filter at approximately 38° C. and low humidity. The percent faderepresents the loss in density at λ_(max) after irradiation.

Dye Diffusion Tests

The released dyes in Table I were also subjected to the conditions oftwo different dye diffusion tests. One, the "solution test" involveddissolving the dye in a viscous composition and transferring it though areceiving element which contains an opaque and reflecting layer inaddition to the mordant layer. The other, a "gel pad test" involvedimbibing the dye from solution into a thick gelatin layer, and thentransferring it by direct lamination to the same receiving element whichhad been preswollen by soaking 5 minutes in a solution of 0.1 potassiumhydroxide. The receiver for these tests had the following composition(coverages are parenthetically given in g/m²):

A transparent poly(ethylene terephthalate) film support coated with

(1) a mordant layer ofpoly(styrene-co-N-vinylbenzyl-N-benzyl-N,N-dimethylammoniumchloride-co-divinylbenzene) (2.28) and gelatin (2.28);

(2) an opaque and reflecting layer of carbon black (1.88) in gelatin(1.23) and titanium dioxide (16.1) in gelatin (2.63); and

(3) an overcoat layer of gelatin (4.3).

Solution Test

Approximately 0.075 mmol of the unmetallized released dye was dissolvedin 10 ml of 0.125N potassium hydroxide. After the dye was completelydissolved, 20 ml of a viscous composition was added; and the resultingsolution, stirred for at least 20 minutes, was 0.0025M in dye at a pH of13.4. The viscous composition was prepared from 46.2 g potassiumhydroxide and 54 g carboxymethylcellulose dissolved in 1200 ml water.The dye solution was then spread between the receiver and a clearpolyester cover sheet between spaced rollers so that the gap containingthe viscous solution had a thickness of 102 μm. Measurement of the rateof dye diffusion was commenced at the point at which half of thelaminate had passed through the rollers. The appearance of dye on themordant was measured at λ_(max) as diffuse reflection density vs. time.The reflection density was converted to transmission density by computerwith the aid of a mathematical relation derived from a previouscalibration. A plot of transmission density, which is proportional toconcentration vs. time, was derived; and the value of t-1/2 of dyetransfer, the time in seconds required to obtain one-half of the maximumtransmission density, calculated.

Gel Pad Test

A donor element, containing a thick pad of deionized acid-processedgelatin (26 g/m²) hardened with 2 percent bis(vinylsulfonylmethyl)ether,was imbibed with a solution of 0.1M in potassium hydroxide and 1.3×10⁻³M in dye. The pad was soaked to full penetration, surface wiped, andthen laminated in direct contact to the above receiving element whichhad been presoaked for 5 minutes at 0.1M KOH. The t-1/2 of dye transferwas obtained as in the solution test. The diffusion times by the "gelpad test" are substantially longer than by the "solution test". Theresults obtained are shown in Table I.

For comparison, the 2:1 nickel complex of2-(2-pyridylazo-4-sulfamoyl-1-naphthol, the chromophore of which isdescribed in U.S. Pat. No. 4,207,104, has solution and gel pad dyediffusion t-1/2 values of 49 and 281 sec., respectively. The 2:1 nickelcomplex of 2-(5-sulfamoyl-2-pyridylazo)-5-(N-methylanilino)phenol, thechromophore of which is described in Anderson et al U.S. Pat. No.4,357,410, has solution and gel pad dye diffusion t-1/2178 values of 45and 265 sec., respectively. The dyes of the invention thus have fastdiffusion times, especially in comparison to these two dyes of the priorart.

                                      TABLE I                                     __________________________________________________________________________    Released Dyes                                                                  ##STR17##                                                                                              Spectra of NiDye Complexes                                                                       Dye                                                        Dye                Diffusion                                                  Solution                                                                              Mordant    t.sub.1/2  (sec)                                           λ.sub.1/2                                                                  HBW λ.sub.1/2                                                                  HBW %     Gel                           Cmpd.                                                                             D   E        Z.sup.1                                                                         Z      (nm)                                                                              (nm)                                                                              (nm)                                                                              (nm)                                                                              Fade                                                                             Soln.                                                                            Pad                           __________________________________________________________________________    A   Cl  SO.sub.2 NHm-                                                                          H H      548 70  553 76  2  41 183                                   C.sub.6 H.sub.4 SO.sub.2 NH.sub.2                                     *A' Cl  SO.sub.2 NHm-                                                                          H H      545 68  555 85  3  -- 235                                   C.sub.6 H.sub.4 SO.sub.2 NH.sub.2                                     B   Cl  SO.sub.2 NH.sub.2                                                                      H H      543 65  545 67  0  31 108                           *B' Cl  SO.sub.2 NH.sub.2                                                                      H H      544 68  546 71  4  -- 161                           C   OCH.sub.3                                                                         SO.sub.2 NHt-C.sub.4 H.sub.9                                                           H H      560 79  563 82  -- 37 --                            D   Cl  SO.sub.2 NH                                                                            H H      543 68  547 66  -- 44 --                                    CH(CH.sub.3).sub.2                                                    E   Cl  SO.sub.2 NHm-                                                                          H H      544 65  550 70  1  39 --                                    C.sub.6 H.sub.4OH                                                     F   Cl  SO.sub.2 N(CH.sub.3)m-                                                                 H H      543 68  546 66  0  69 --                                    C.sub.6 H.sub.4 OH                                                    G   Cl  SO.sub.2 NHC.sub.6 H.sub.5                                                             H H      542 65  548 70  0  81 --                            H   Cl  SO.sub.2 NHCH(CH.sub.3).sub.2                                                          Cl                                                                              CONHm- 548 63  549 72  7  49 --                                               C.sub.6 H.sub.4OH                                          I   Cl  SO.sub.2 NH.sub.2                                                                      Cl                                                                              CONHm- 545 62  550 70  4  57 --                                               C.sub.6 H.sub.4OH                                          J   OCH.sub.3                                                                         SO.sub.2 NHm-                                                                          H H      559 78  568 87  0  40 --                                    C.sub.6 H.sub.4OH                                                     __________________________________________________________________________     *premetallized compound, alternative receiving element                   

EXAMPLE 2 Comparative Spectra

Example 1 was repeated to obtain spectrophotometric data on mordantedstrips for the following:

(a) a 2:1 nickel complex of 2-(2-pyridylazo)-4-sulfamoyl-1-naphthol, thechromophore of which is described in Dye 26 of U.S. Pat. No. 4,207,104of Chapman et al (Control Dye 1);

(b) a 2:1 nickel complex of2-(5-sulfamoyl-2-pyridylazo)-5-(N-methylanilino)phenol, the chromophoreof which is described in Compound D of U.S. Pat. No. 4,357,410 ofAnderson et al (Control Dye 2);

(c) a 2:1 nickel complex of6-(2-carboxy-4-chlorphenylazo)-2,3-pyridinediol, the chromophore ofwhich is described in Compound 32 of U.S. Pat. No. 4,287,292 of Chapmanet al (Control Dye 3); and

(d) a 2:1 nickel complex of Compound C.

The absorption envelope of each of the metallized dyes is described by(1) the wavelength(s), λ_(max), at the actual D_(max), (2) the λ_(1/2)which is the mean of the wavelength limits of the absorption envelope athalf the maximum density, nd (3) the halfband width (HBW) which is theband width at half the D_(max). A narrow HBW generally designates apurer hue. The following results were obtained.

                  TABLE II                                                        ______________________________________                                                    λ.sub.max                                                                       λ.sub.1/2                                                                     HBW                                                           (nm)     (nm)   (nm)                                              ______________________________________                                        Control Dye 1 553, 567   537    101                                           Control Dye 2 540, 572   540    116                                           Control Dye 3 555        545    86                                            Compound C    560        545    67                                            ______________________________________                                    

The above results indicate that the metal dye complex of the inventionhas a substantially narrower band width and less unwanted absorptionthan any of the prior art metallized dyes. It will therefore provide amore accurate color reproduction than the broader absorbing metallizeddyes of the prior art.

EXAMPLE 3 Synthesis of Compound 3

To a solution of 5.5 g (12.1 mmol) Compound E in 200 ml tetrahydrofuran,100 ml pyridine and 4.8 g (37.2 mmol) N,N-diisopropylethylamine wasadded 3.0 g (3.17 mmol)3,6-bis(1-p-t-butylphenylethyl)-2,5-bis(N-n-dodecylchloroformamidomethyl)benzoquinone(see U.S. Pat. No. 4,204,870, Col. 31). After stirring for 1 hour, anadditional 2.5 g (2.64 mmol) of the acid chloride is added and thereaction stirred 28 hours at room temperature. The crude reactionmixture was concentrated to ca. 100 ml in vacuo at 40° C. and theresidue was partitioned between ethyl acetate and 3N HCl. The layerswere separated, the organic phase washed with 3N HCl (until washingswere acidic), water and saturated sodium chloride solution. After drying(MgSO₄) the organic phase was evaporated in vacuo and the residuerecrystallized twice from 350-400 ml ethanol. Yield 7.5 g (72 percent)of yellow solid: ε⁵⁵⁰ =13.0×10⁴ (3:1 dioxane-pH 6 buffer+excess Ni²⁺).

Intermediates Compound E,8-[3-Chloro-5-(m-hydroxyphenylsulfamoyl)-2-pyridylazo]-5-quinolinol

A solution of 5.0 g (31.4 mmol) quinoline-5,8-quinone [T. Urbanski andS. Krzyzanowski, Roczniki Chem., 27, 390 (1953); Chem. Abstr., 49, 1041b(1955)] in 50 ml ethyl alcohol and 100 ml tetrahydrofuran was chilled to<5° C. Concentrated HCl (1 ml) and a cold slurry of 10.0 g (31.8 mmol)3-chloro-5-(m-hydroxyphenylsulfamoyl)-7-pyridylhydrazine in 100 ml ethylalcohol/0.5 ml concentrated HCl were added in that order. The reactionwas stirred at 0°-10° C. for 18 hours. The crude product was collectedby filtration and dried to yield 5.8 g of an orange solid. Concentrationof the filtrates afforded an additional 2.6 g of less pure material. Thecrude product was purified by recrystallization from CH₃ CN to yield 6.1g (43 percent) of a yellow-orange solid: ε⁵⁵⁰ =6.6×10⁴ (3:1 dioxane-pH 6buffer+Ni²⁺).

EXAMPLE 4 Synthesis of Compound 14

N,N-Di-n-octadecyl-4-(2-hydrazino-3-chloro-5-pyridinesulfonamido)-1-hydroxy-2-naphthamide(4.56 g; 0.005 mole) (U.S. Pat. No. 4,357,412, issued Nov. 2, 1983,Example 2), acetone (15 ml) and conc. hydrochloric acid (2 drops) weremixed and heated at boiling for a couple minutes. On cooling andscratching the hydrazone crystallized. More methanol was added (100 ml)and after cooling in ice the hydrazone was filtered, washed with alittle methanol, and dried to give 3.37 g (70.7 percent) of the acetonehydrazone.

This hydrazone, benzoyl chloride (1.05 g; 0.0075 mole), triethylamine(0.81 g; 0.008 mole), and pyridine (50 ml) were stirred under nitrogenin a flask with a condenser at room temperature over the weekend.Evaporation of the pyridine gave a syrup which could not be made tocrystallize upon treatment with aqueous methanol.

The above syrup, which probably comprised a mixture of benzoylatedproducts was treated with warm methanol-ether containing some conc.hydrochloric acid for a few minutes. After cooling to room temperatureand adding more ether if necessary to maintain solution,5,8-quinolinequinone (0.56 g; 0.0035 mole) was added followed by an hourof stirring. The solution, which was now orange, was transferred to aflask and degassed by bubbling nitrogen through the stirring solution.Methanolic potassium hydroxide was then added until a deep magenta colorwas maintained. After stirring two hours or so at room temperature,hydrochloric acid was added until the magenta color was gone. The liquidwas partially evaporated to remove ether, diluted with water, stirred anhour, and the gummy solid was filtered.

Since the crude product would not become crystalline, and its purity wasunknown, it was dissolved in methanolic ether and treated with an excessof nickel acetate in methanol. After stirring 30 min. the solution wasdiluted with water and stirred for an hour allowing a small ether layerto evaporate. The product was filtered and allowed to dry. The crudeproduct was dissolved in ether and filtered to remove excess nickelacetate and any other inorganic salts. The ether solution was dilutedwith a methanol/ethanol (1:1) mixture and stirred for an hour as themetallized product separated. It was filtered and air dried to give 1.8g as a purple powder. The analytical data suggested that the product wasa mixture of the 2:1 complex shown and the acetate of the 1:1 complex.

Calculated for the 2:1 complex: C, 67.7; H, 8.2; N, 7.8; Cl, 3.3; S,3.0; Ni, 2.7;

Calculated for the 1:1 complex (acetate): C, 64.6; H, 7.8; N, 7.2; Cl,3.0; S, 2.7; Ni, 5.0;

Found: C, 65.5; H, 8.2; N, 7.4; Cl, 2.4; S, 2.5; Ni, 3.4.

EXAMPLE 5 Photographic Test

A photographic element was prepared by coating the following layers inthe order recited on a transparent poly(ethylene terephthalate) filmsupport. Coverages are parenthetically given in g/m² unless otherwisestated.

(1) DRR layer of Compound 14 (2.2×10⁻⁴ moles/m²) in 1/2 its weight ofdiethyllauramide, potassium 5-s-octadecylhydroquinone-2-sulfonate(0.022) and a blocked developing agent1-phenyl-2-pyrazolin-3-yl-N-methyl-N-[2-(N-methyltrifuloroacetamidomethyl)-4-(p-sulfonamido)phenyl]carbamate(0.54) in gelatin (2.8);

(2) Green-sensitized silver chloride emulsion (0.39) in deionizedgelatin (0.86), 1-(m-acetamidophenyl-2-tetrazoline-5-thione (350 mg/moleAg), and octadecylquinone (5 g/mole Ag); and

(3) overcoat layer of 2,5-di-s-dodecylhydroquinone (0.32) in deionizedgelatin (0.54).

A receiving element was prepared by coating a mordant layer of a mixtureof poly(N-vinylimidazole) (1.6 g/m²) and gelatin (1.6 g/m²) coated overa gelatin layer (0.81 g/m²) containing nickel sulfate (0.11) on apolyethylene-coated paper support.

The photographic element was given a full exposure to D_(max), thensoaked for 15 seconds in an activator containing per liter of developer:33.7 g potassium hydroxide, 2.0 g potassium bromide, 3.0 g5-methylbenzotriazole, and 2.0 g 11-aminoundecanoic acid. Thephotographic element was then laminated to the receiver. The laminatewas then cut into four pieces and placed on a constant temperature (24°C.) block. The four receiver pieces were peeled off after 1, 3, 5 and 10minutes, each dried and the Status A density recorded. The access time,taken as the first of the strips to achieve a constant density on thereceiver, was 5 min. at a green density of 0.75. When the receiver wasirradiated for 28 days with a 6000 W Xenon arc lamp at 50 Klux through aWratten 2B (ultraviolet) filter, the density loss was only 0.14.

The invention has been described in detail with particular reference topreferred embodiments thereof, but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention.

What is claimed is:
 1. A nondiffusible compound capable of releasing atleast one diffusible magenta dye moiety, said compound having theformula: ##STR18## wherein: (a) X represents the atoms necessary tocomplete a 5- or 6-membered heterocyclic ring;(b) Y represents the atomsnecessary to complete a 5- or 6-membered heterocyclic fused ring; (c)CAR represents a ballasted carrier moiety which will release saiddiffusible magenta dye moiety as a function of development of a silverhalide emulsion layer under alkaline conditions; (d) R representshydroxy, a salt thereof, or a hydrolyzable precursor thereof, or CARwhich is linked to said dye moiety through an oxygen atom thereon; and(e) n is 0, 1 or 2, with the proviso that when n is 0, then R is CARwhich is linked to said dye moiety through an oxygen atom thereon. 2.The compound of claim 1 wherein said CAR will release said diffusiblemagenta dye moiety from said nondiffusible compound as an inversefunction of development of a silver halide emulsion layer under alkalineconditions.
 3. The compound of claim 2 wherein said CAR is a grouphaving the formula: ##STR19## wherein: Ballast is an organic ballastingradical of such molecular size and configuration as to render saidcompound nondiffusible in a photographic element during said developmentin an alkaline processing composition;W² represents at least the atomsnecessary to complete a quinone nucleus; r is a positive integer of 1 or2; R⁴ is alkyl having 1 to about 40 carbon atoms or aryl having 6 toabout 40 carbon atoms; and k is a positive integer of 1 to 2 and is 2when R⁴ has less than 8 carbon atoms.
 4. The compound of claim 1 whereinR is hydroxy and X represents the atoms necessary to complete apyridine, imidazole or pyrazole ring.
 5. The compound of claim 1 whereinR is hydroxy and Y represents the atoms necessary to complete aquinoline, quinoxaline or benzimidazole ring.
 6. The compound of claim 1wherein R is hydroxy, X represents the atoms necessary to complete apyridine ring, Y represents the atoms necessary to complete a quinolinering, n is 1 and CAR is attached to the pyridine ring.
 7. The compoundof claim 1 wherein CAR is a group having the formula:

    (Ballast-Carrier-Link)--

wherein: (a) Ballast is an organic ballasting radical of such molecularsize and configuration as to render said compound nondiffusible in aphotographic element during development in an alkaline processingcomposition; (b) Carrier is an oxidizable acyclic, carbocyclic orheterocyclic moiety; and (c) Link represents a group which, uponoxidation of said carrier moiety, is capable of being hydrolyticallycleaved to release said diffusible dye.
 8. The compound of claim 7wherein the Carrier moiety contains atoms according to the followingconfiguration:

    a(--C═C).sub.b --

wherein: b is a positive integer of 1 to 2; and a represents theradicals OH, SH, NH- or hydrolyzable precursors thereof.
 9. The compoundof claim 1 wherein CAR is a group having the formula: ##STR20## wherein:(a) Ballast is an organic ballasting radical of such molecular size andconfiguration as to render said compound nondiffusible in a photographicelement during development in an alkaline processing composition;(b) Dis OR¹ or NHR² wherein R¹ is hydrogen or a hydrolyzable moiety and R² ishydrogen or substituted or unsubstituted alkyl of 1 to 22 carbon atoms;(c) Z represents the atoms necessary to complete a benzene nucleus, anaphthalene nucleus, or a 5 to 7 membered heterocyclic ring; and (d) jis a positive integer of 1 to 2 and is 2 when D is OR¹ or when R² ishydrogen or alkyl of less than 8 carbon atoms.
 10. The compound of claim9 wherein D is OH, j is 2 and Y is a naphthalene nucleus.
 11. Thecompound of claim 2 wherein said CAR is a group having the formula:##STR21## wherein: Ballast is an organic ballasting radical of suchmolecular size and configuration as to render said compoundnondiffusible in a photographic element during said development in analkaline processing composition;W¹ represents at least the atomsnecessary to complete a benzene nucleus; and R³ is alkyl having 1 toabout 4 carbon atoms.
 12. The compound of claim 2 wherein said CAR is agroup having the formula: ##STR22## wherein: Ballast is an organicballasting radical of such molecular size and configuration as to rendersaid compound nondiffusible in a photographic element during saiddevelopment in an alkaline processing composition;W¹ represents at leastthe atoms necessary to complete a benzene nucleus; and R³ is alkylhaving 1 to about 4 carbon atoms.
 13. The compound of claim 2 whereinsaid CAR is a group having the formula: ##STR23## wherein: Ballast is anorganic ballasting radical of such molecular size and configuration asto render said compound nondiffusible in a photographic element duringsaid development in an alkaline processing composition;W¹ represents atleast the atoms necessary to complete a benzene nucleus; r is a positiveinteger of 1 or 2; R⁴ is alkyl having 1 to about 40 carbon atoms or arylhaving 6 to about 40 carbon atoms; k is a positive integer of 1 to 2 andis 2 when R⁴ is a radical of less than 8 carbon atoms; and K is OH or ahydrolyzable precursor thereof.
 14. The compound of claim 1 wherein saiddye-releasing compound is: ##STR24##
 15. The compound of claim 1 whereinsaid dye-releasing compound is: ##STR25## wherein R⁵ is ##STR26##